Insecticide and fungicide



Patented June 30, 1936 UNITED STATES INSECTICIQE AND FUNGICIDE Theron. P. Remy, Les Angcles, Calif., assignor to The Texas Company, New YorlnN. Y., a corporation of Delaware No Drawing.

Application October 15, 1932, .Serial No. 637,991

7 Claims. (Cl. 167-22) This invention relates to insecticides and fungicides and more particularly to insecticides and fungicides in the form of solutions 'of organic sulfur compounds in liquid solvents.

This invention contemplates the manufacture of insecticides and fungicides by dissolving in a suitable organic carrier liquid varying percentages of certain groups of organic sulfur compounds recovered from petroleum, or the prod- 10 ucts obtained bycracking petroleum.

All crude 'oils contain some compounds of sulfur -which are more or less undesirable insofar as the general commercial use of the refined, petroleum products is concerned. During the processes of distillation, cracking and refining.

these compounds may be altered in chemical constitution, and the synthesis of new organic sulfur compounds may occur. It is desirable to re, move these sulfur compounds during the refining processes.

A study of the sulfur compounds contained in petroleum reveals some of them to be highly toxic to insect and fungus life. Among the more toxic sulfur compounds found in petroleum or its derivatives are the mercaptans, the thiophenols and thiocresols, the alkyl sulfides or thio ethers, the disulfides, the thiophenes, the sulfones, the sulfoxides and the sulfonic acids.

These organic sulfur compounds may be separated from petroleum or its derivatives or from the products of the cracking and refining processes by well-known chemical reactions.

It is known that freshly distilled naphthas contain sulfur compounds of the mercaptan, thiophenol and thiocresol classes, which are readily acted upon by caustic soda. This reagent is usually used in the formof a solution with which the untreated naphthas are washed, and with which the organic sulfur compounds react to I form the corresponding sodium salts. By acidification of the separated sodium salts it ispossible to bring about their reconversion to the original,

corresponding mercaptans, thiophenols and'thiocresols.

15 Disulfides are produced when mercaptans are subjected to the doctor treatment. This consists principally in reacting them'with sodium plumbite and sulfur. Recovered mercaptans may in this manner be converted into the corresponding disulfides.

Organic sulfides are present as such in some petroleum distillates and in the products obtained by cracking petroleum, though they may be obtained more readily from the tars and sludges resulting from the sulfuric acid treatment of segregate certain sulfur and oxygen compounds these materials. A method that is applicable for this purpose is the formation of double compounds with heavy metal salts.

Sulfones and sulfoxides are compounds which correspond to the formulae 5 R R SO and SOz n 1/ respectively, and usually result when organic sulfides are subjected to oxidizing conditions, as in treating the petroleum sulfides with sodium hypochlorite or sodium peroxide.

'I'hiophcne and sulfonic acids are best obtained by their separation from sulfuric acid tars and sludges. Distillation by means of steam is one method that is useful for this purpose.

In refining certain light fractions of petroleum such as naphtha and kerosene by means of selective solvents, it has been found possible to whose presence in the final products is undesirable. Analyses of the extracts prepared, for example, by treating low boiling petroleum hydrocarbons with selective'solvents such as sulfur dioxide, furfural and the like, have indicated that these extracts contain large proportions of organic sulfur and organic oxygen compounds. When these compounds are dissolved in suitable solvents the resulting liquids are extremely potent and toxic insecticides and fungicides.

Although it is feasible to use certain or all of the above enumerated sulfur compounds in a pure form without the addition of any other material and applying them in the form'of sprays or-i-n a finely divided form, the vapor pressures of these compounds are usually so high as to result in the rapid vaporization of the compounds. Such a condition is highly undesirable since it militates against the contacting of the insect or fungus 40 with a sufiiciently high concentration of the sulfur compound to have the desired toxic effect.

I have found that when the organic sulfur compounds recovered from petroleum, from its derivatives or from the products obtained by cracking 45 petroleum, are used in conjunction with a suitable solvent for the sulfur compounds, highly emcient and toxic insecticides and fungicides result. The

I most desirable solvents are those which have low vapor pressures and which may therefore be at- 5 omized into a finely divided form without vaporizing in the atmosphere. When an organic sulfur compound, or a mixture of organic sulfur compounds, such as those enumerated above, is dissolved in such a solvent and the resultant solu- 55 tion is atomized, an extremely stable fog results. The sulfur compounds appear to vaporize quite slowly from the respective liquid particles of sol-\ vent in which they are dissolved and therefore have a long continued toxic effect. By applying the organic sulfur compounds in this manner, the deleterious effects on plant life which may result from the application of the undiluted organic sulfur compounds are averted.

It has been established that sulfur compounds, such as are found in petroleum derivatives or in the products obtained by cracking petroleum, are selectively soluble in highly polar inorganic solvents such as liquid sulfur dioxide, liquid ammonia and sulfuric acid. The solubility of the sulfur compounds is not, however, limited to the inorganic polar solvents since they are also highly soluble in organic polar solvents. These include the following classes of compounds,alcohols, aldehydes, ketones, esters, amines and organic acids.

Most petroleum hydrocarbons, not being sufliciently refined to remove all of the unsaturated and aromatic compounds present therein, are definitely polar in reaction and therefore exert a solvent action on organic sulfur compounds. However, in those cases where the petroleum hydrocarbons are highly refined, that is to say, where substantially all the unsaturated and aromatic compounds have been completely removed, solvent action for organic sulfur compounds may be quite low, in which case, the solvent action for the sulfur compounds may be increased by the judicious admixture thereto of phenols, alcohols and, in fact, any polar hydrocarbon.

From the above, it is apparent that any polar organic liquid may be used as a solvent for the sulfur compounds in the preparation of the insecticides and fungicides and, in some cases, it may be desirable to step up the polarity of the solvent by dissolving therein highly polar compounds such as organic acids, phenols or the like.

In preparing the insecticides and fungicides according to the present invention, solution of the proper quantity or percentage of the sulfur compounds may be effected in any satisfactory .man-

ner. For example, in forming an insecticide containihg mercaptan bodies, I have found it advisable to wash the water solution containing the liberated mercaptans with an organic solvent whereby the mercaptans are dissolved. The quantities of sulfur compound or sulfur compounds dissolved in the carrier liquids may vary widely about 5% of a liquid member of the disulflde series depending upon the desired use to which the resultant insecticide or fungicide is to be put.

The present invention therefore is not limited to the use of any specific percentages of the sulfur compounds in the carrier liquids. I have com- 5 pounded satisfactory insecticides containing varying percentages of the sulfur'compounds with certain petroleum hydrocarbons. For example, an insecticide formed by dissolving 5% of ethyl mercaptan in a kerosene distillate when used in an atomized'fog was found to kill substantially all the insect lift infesting stored grains.

A solution containing .5% of thiopliene and 99.5% of naphthenic acids, when atomized to produce a fog, will give a very eflicient kill of the insects infesting citrus trees. A fly spray, prepared by dissolving .2% of ethyl disulfide in a carrier liquid consisting of a kerosene distillate containing 1% of phenols, will give a quantitative kill of household flies and insects.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

- 1. A liquid insecticide and fungicide comprising a kerosene distillate containing in solution about 5% of a liquid member of the mercaptan series of compounds recoverable from petroleum and the products of refining the same.

2. A liquid insecticide and fungicide comprising a kerosene distillate containing in solution of compounds recoverable from petroleum and the products of refining the same.

3. An insecticide and fungicide in the form of a readily atomizable liquid consisting essentially of a polar organic carrier liquid and a liquid organic sulfur compound recoverable'from petroleum and the products of refining the same selected from thefgroup consisting of mercaptans and disulfldes.

4. -A composition of matter in accordance with claim 3 in which the polar organic carrier liquid comprises naphthenicacids.

5. A composition of matter in accordance with claim 3 in which the polar organic carrier liquid comprises phenol. 

